143
J. Chem. Eng. Data 1992, 37, 143-145
K k n P R T V V
v X
Y z
&e& cp w
vaporization equilibrium ratio, ylx binary interaction parameter number of moles pressure universal gas constant temperature total volume molar volume partial molar volume mole fraction in the liquid phase mole fraction In the vapor phase mole fraction (liquid or vapor phase) Letters fugaclty coefficient acentric factor
critical property components i and j reduced property
C
ij r
Reglrtry No. COP, 124-38-9; phenol, 108-95-2; catechol, 120-80-9.
Literature Cited Tsai, F. N.; Yau, J. S. J . Chem. Eng.Data 1990. 35, 43. Yau, J. S.; Tsai, F. N. J . (2".Eng. Data, in press. Krichevsky, I . R.; Iiinskaya, A. A. Zh. Flz. Khhn. 1945. 19, 621. Huang. S. H.; Lin, H. M.; Tsai. F. N.; Chao, K. C. Ind. Em. Chsm. Res.-l988, 27, 182. Graboski, M. S.; Daubert, T. E. Ind. €ng. Chem. Frocess Des. Dev. ism. .- .-, 17. . 443. . .Reid, R. C.; Prausnltz, J. M.; Poling, B. E. Tho R@wtf&s of Qamand Liquids, 4th ed.; McGrawHiil: New York, 1988. Ambrose, D. C o " and Esttmetkm of Vapw-Uquld Crkal ert&s I . Critical Temperahnes of &@nk ; NPL Rep. Chem. 9 2 Natlonai Physical Laboratory: Tedlngton, Sept 1978; corrected March 1980. Ambrose. D.CwrelarrOn and €slknaHon of Vapw-uquld Mica/ R q ert&s I I . Critkxl Pressures and Volumes of &@nk CompocnrdP; NPL Rep. Chem. 98; National Physical Laboratory: Teddington, 1979. Lee, B. I.; Kesier, M. (3. A I M J . 1975, 21, 510. Bender, E.; Klein. U.; Schmkt, W.; Prausnitz, J. M. FMd phese E q M . 1984, 15, 241.
.
m-
.
Superscripts L liquid phase S saturated property m Infinite dilution
.
Subscripts 1 component 1 (solvent) 2 component 2 (solute)
Received for review February 10, 1991. Revised June 13, 1991. Accepted February 5, 1992. Acknowledgment is made to the National Science COuncW of the Republic of China (Grant NSC 79-0402I006-17) for flnanclal support of this work.
Isobaric Vapor-Liquid Equilibria for the Binary Systems CH3SiHC12 with (CH3)3SICI, (CH3)2SiC12,CH3SiC13,or SiCI4 Trandaflr Ruglni and Llvlu Sic6rescu Institute of Macromolecular Chemistry "P. Poni", Aleea &&or@ ohica V d 4 lA, 6600 Iaqi, Romania The physicochemical constants of the purified substances are compared with literature data in Table I. w a h m and he".The expeh.lental apparatus was a Swietoslawskl-type ebullometer ( 1 ) . The experimental boiling temperatures, t ', were measwed to within 5.10-2 OC with a Beckmann thermometer calibrated in our laboratory with benzene for high boiling points and CH,HSICI, for low boiling points. The atmospheric pressure, P', was read on a Hg barometer to within 0.1 mmHg. The liquld, x,, and vapor, y,, mole fraction compositions of the two phases at equilibrlum were determined by means of a gas chromatograph (2) packed with a mixture of 70% FS 1265 30% SE-30 on AW/DHCS Chromosorb P, 60-80 mesh. The overall uncertainty In the equfflbrium mole fractions is estimated The t o values at pressure P' were to be (0.1-1) X corrected for normal pressure, P o = 760 mmHg, using the foliowing equation (3):
Thk paper reports isobaric vapor-liquid equlllbrlum (VLE) data for four binary systems containing dkhloromdhykllane, CH3S1HCi,, and chlorotrlmethyl-, dkhlorodlrmthyl-, trlchloromethyl-, or tetrachlorosllane, (CHs),-,SiCi, ( n = 1-4). The VLE data were determined ~ l ~ t r l c a at H atmospheric y pressure, and the experhnental tmpwatuns were corrected for 760 mmHg. The pure component vapor pressures were calculated using Uteratwe Antdne constants. The VLE data were then corrdated by means of the Wikon, nonrandom twdlquid (NRTL), and Gothard equations.
+
Introduction Vapor-liquld equilibrium (VLE) data for binary methylchlorosilane systems are scarce. I n view of the importance of these data for the design of rectification columns in manufacturing silicon derivatives, we developed a data base for this class of substances. All the VLE data published until now on methylchiorosllanes were tested using a rectification process computer simulator and were verified on an industrial pilot plant.
t
=
t'
+ ((dtl/dP)X, + (dt,/dP)X,)(PO - P')
(1)
where t, is the boiling temperature of pure component icalculated with the Antolne equation from t,/OC = B , / [ A , - log (Po/mmHg)]
- C,
Expertmental Section
The experimental data are shown in Tables 11-V.
M a w . The methylchiorosilanes were Fluka products wtth 98% stated purtty. They were purified by distillation on a laboratory column until no Impurities were chromatographically detectable.
Rnuits
(2)
The liquld-phase activity coefficients, T,, were calculated from the experimental P-x-y data at each temperature. The 0
1992
Amerlcen Chemical Society
144 Journal of Chemical and Engineering Data, Vol. 37, No. 2, 1992
Table I. Densities, Normal Boiling Points t , and Antoine Coefficients A , B , and C, Equation 2 (3), for Methylchlorosilanes ~ ( 2 0" C ) / k t/oc component exptl lit. (8, 9) exptl lit. (8, 9) A B C 41.60 41.0 7.0484 1179 242.00 1.110 1.1069 CH3SiHC12 56.63 57.2 6.9728 1200 1.483 235.96 SiC1, 1.479 57.2 6.9505 0.858 57.14 1191 235.05 0.859 (CH3)3SiC1 65.34 6.8721 1167 65.38 226.00 1.273 1.276 CH3SiC13 70.00 7.1435 1328 241.05 1.0663 69.37 (CH3)2SiC12 1.069 Table 11. Experimental Boiling Temperature t* at Pressure P*,Corrected Boiling Temperature t at Normal Pressure (P = 760 mmHg), Equation 1, Activity Coefficients y i , Liquid-Phase Mole Fraction xl,and Vapor-Phase Mole Fraction y , for the Binary System CHnSiHClz(l)-SiCl, (2) Ye t*l°C P / m m H g tl°C t*/OC P / m m H g t / o c Y1 X1 Y1 X1 Y1 Y1 Yz 54.44 54.30 53.94 53.34 52.47 51.40 50.86 50.35 48.29 47.43
745.5 745.5 745.5 745.5 745.5 745.5 745.5 745.5 745.5 745.5
55.03 54.89 54.43 53.93 53.06 51.99 51.45 50.94 48.87 48.01
0.0204 0.0253 0.0426 0.0618 0.0962 0.1402 0.1637 0.1868 0.2867 0.3335
0.0461 0.0567 0.0923 0.1294 0.1917 0.2611 0.2944 0.3259 0.4416 0.4894
1.4687 1.4612 1.4311 1.4038 1.3701 1.3215 1.2966 1.2766 1.1995 1.1732
1.0445 1.0427 1.0364 1.0305 1.0211 1.0154 1.0144 1.0134 1.0241 1.0315
46.13 44.72 44.29 43.77 42.54 41.78 41.33 41.30 40.70
745.5 745.5 745.5 745.5 745.5 745.5 745.5 744.8 744.8
46.71 45.30 44.87 44.34 43.11 42.35 41.90 41.89 41.29
0.4103 0.5082 0.5431 0.5898 0.7274 0.7697 0.8680 0.8695 0.9385
0.5583 0.6369 0.6634 0.6981 0.7923 0.8244 0.9001 0.9015 0.9539
1.1321 1.0892 1.0761 1.0603 1.0144 1.0220 1.0038 1.0040 1.0035
1.0531 1.0890 1.1026 1.1217 1.2121 1.2454 1.2565 1.2536 1.2719
Table 111. Experimental Boiling Temperature t* at Pressure P*,Corrected Boiling Temperature t a t Normal Pressure (P = 760 mmHg), Equation 1, Activity Coefficients y,, Liquid-Phase Mole Fraction x,,and Vapor-Phase Mole Fraction y 1 for the Binary System CHnSiHCl,(1HCHASiCl (2) t*/OC P / m m H g t/'C xl Y1 Y1 Yz t*/OC P / m m H g t/OC x1 Y1 Y1 Yz 77.20 56.30 55.90 55.30 54.50 53.90 52.70 51.90 50.80 48.90
750.6 750.6 750.6 750.7 750.7 751.2 751.2 751.2 751.6 751.6
57.58 56.68 56.28 55.68 54.88 54.30 53.05 52.25 51.14 49.23
0.0522 0.0997 0.1490 0.2029 0.2616 0.3167 0.4055 0.4720 0.5139 0.6065
0.0751 0.1366 0.2045 0.2777 0.3551 0.4248 0.5301 0.6027 0.6458 0.7331
0.8212 0.8482 0.8590 0.8711 0.8838 0.8879 0.8973 0.8972 0.9127 0.9299
0.9796 0.9866 0.9737 0.9618 0.9506 0.9333 0.9120 0.8910 0.8943 0.8861
47.73 46.40 45.30 44.00 43.50 42.85 42.50 42.30 41.85
751.6 751.6 751.6 751.6 751.6 751.6 751.5 751.5 751.5
48.03 46.73 45.63 44.33 43.83 43.18 42.83 42.63 42.18
0.6537 0.7419 0.7876 0.8624 0.8990 0.9323 0.9345 0.9463 0.9822
0.7737 0.8424 0.8749 0.9235 0.9454 0.9643 0.9655 0.9720 0.9910
0.9445 0.9432 0.9550 0.9591 0.9569 0.9609 0.9706 0.9712 0.9679
0.8882 0.8670 0.8679 0.8563 0.8471 0.8450 0.8542 0.8515 0.8388
Table IV. Experimental Boiling Temperature t * at Pressure P*,Corrected Boiling Temperature t at Normal Pressure (P = 760 mmHg), Equation 1, Activity Coefficients y,, Liquid-Phase Mole Fraction xl,and Vapor-Phase Mole Fraction y , for the (2) Binary- System CH.SiHC1,_(l)CH,SiCl, .. t*/OC P / m m H g t/OC x1 Y1 Y1 Yz t*/OC P / m m H g t/OC zl Y1 Y1 YZ I
66.04 65.52 64.45 64.67 63.79 61.40 59.80 56.40 55.40
753.0 753.0 753.6 753.6 754.1 754.1 754.1 754.1 754.1
66.33 65.81 65.72 64.87 64.04 61.64 60.04 56.64 55.64
0.0102 0.0263 0.0337 0.0629 0.0952 0.1801 0.2492 0.3787 0.4419
I
.
.
0.0188 0.0481 0.0615 0.1135 0.1689 0.3055 0.4057 0.5679 0.6351
0.8734 0.8786 0.8787 0.8870 0.8932 0.9113 0.9139 0.9265 0.9138
0.9930 0.9948 0.9910 0.9907 0.9865 0.9801 0.9635 0.9446 0.9178
53.35 48.78 46.80 44.95 44.16 43.02 42.32 41.80
754.1 753.8 753.4 753.4 753.4 745.7 746.1 746.5
53.59 49.03 74.06 45.21 44.42 43.58 42.86 42.33
0.5227 0.6953 0.7712 0.8438 0.8795 0.9150 0.9393 0.9608
0.7119 0.8444 0.8912 0.9305 0.9481 0.9645 0.9753 0.9843
0.9193 0.9397 0.9501 0.9605 0.9627 0.9668 0.9743 0.9780
0.9070 0.8962 0.8939 0.8930 0.8892 0.8887 0.8917 0.8917
I
Table V. Experimental Boiling Temperature t* at Pressure P*,Corrected Boiling Temperature t at Normal Pressure (P = 760 mmHg), Equation 1, Activity Coefficients yi, Liquid-Phase Mole Fraction x,,and Vapor-Phase Mole Fraction y , for the Binary System CHISiHClz( 1)-(CHS)2SiC12(2) t*/OC P / m m H g t l o C x1 Y1 Y1 YZ t*/OC P / m m H g t/OC xl Y1 Y1 72 69.51 69.14 68.70 67.06 66.37 64.61 64.61 60.47 59.66 58.11 56.15
751.1 750.9 750.9 751.2 751.7 752.2 752.2 753.4 753.4 753.4 753.4
69.88 69.52 69.08 67.42 66.71 64.93 64.93 60.74 59.93 58.38 56.42
0.0284 0.0384 0.0552 0.1118 0.1354 0.1988 0.2019 0.2239 0.3489 0.3751 0.4269
0.0546 0.0736 0.1052 0.2081 0.2491 0.3531 0.3579 0.3916 0.5609 0.5918 0.6485
0.8293 0.8344 0.8390 0.8554 0.8613 0.8716 0.8699 0.8724 0.8842 0.8875 0.8926
0.9911 0.9921 0.9885 0.9793 0.9752 0.9587 0.9553 0.9490 0.9161 0.9112 0.9004
nonideality of the vapor phase and the Poynting factor were taken into account in terms of the second virial coefficients of
52.85 50.72 48.41 46.47 45.39 44.52 43.71 43.21 42.80 42.10
753.4 755.9 756.2 756.3 756.9 757.3 757.7 757.7 757.5 757.5
53.12 50.88 48.56 46.62 45.51 44.63 43.80 43.30 42.90 42.30
0.5048 0.6098 0.6920 0.7756 0.8383 0.8744 0.9116 0.9369 0.9511 0.9668
0.7232 0.8075 0.8616 0.9078 0.9382 0.9538 0.9687 0.9783 0.9834 0.9889
0.8902 0.9060 0.9108 0.9187 0.9327 0.9412 0.9427 0.9510 0.9568 0.9588
0.8762 0.8652 0.8518 0.8452 0.8427 0.8443 0.8392 0.8403 0.8448 0.8445
the pue components estimated from critical data ( 4 )(Table VI). The excess virial coefficients and the excess molar volumes
Journal of Chemical and Engineering Data, Voi. 37, No. 2, 1992 145
Table VI. Critical Temperature, Tc,Pressure, Pc,and Molar Volume. Vc.of the Pure ComDonents ( 9 ) 'P/K P/atm VC/(cm3 m 7 ' ) component
The optimal parameters were obtained by minimization of the objective function:
~~
CH3SiHC12
SiCl, CH3SiCl (CH3)3SiC13
(CHJ2SiC12
475 507 498 518 520
38.5 37.0 31.6 54.9 34.4
290 330 363 339 350
Table VII. Root Mean Square Deviations of g E / R T ,u*(gE),and y , ZQ),Obtained from the Correlations model Darameter
CH3SiHCl2+ SiCL
(CHd,SiCl
CH,SiCL
(CHASiCI,
Wilson, Equation 3
(A1, - A,,)/(J mol-') (Az1 - X,)/(J mol-')
-709.563 1427.938 2.0 1.7
aij
(g12 - gll)/(J mol-') QZ1 - gZ2) (J mol-') oZ(gE)/lO a26)/ 102
0.3 169.578 62.469 1.9 0.46
nl n2 u2(gE)/102 UZ(y)/102
0.903 1.175 1.9 0.96
.2(93/102 a2(y)/l02
614.5 739.5 1.5 3.4
304.5 947 2.3 3.3
332.0 918.875 2.0 4.8
0.3 -97.688 -93.625 2.3 2.5
0.3 -183.625 -79.563 1.9 3.9
1.05 0.65 2.1 2.0
1.3 1.9
NRTL,Equation 6
/
0.3 -149.563 -94.875 1.3 2.4
Gothard, Equation 8
0.805 0.766 1.5 2.2
of the mixtures were assumed to be zero. The experlmentai data were correlated using the following
Q=
c [(gE/RT),x,tl - @E/RT),,12 N
(10)
Table VI1 presents the root meen square deviations, 62(sE)and &Y), of gEIRTand y,for the studled Mnary systems. From this table one can see that the three models reproduce the binary systems equally well. The results presented in Tables I I-V show that the deviations from ideality are small. The system MeHSK;I,-SK=l, has a slight posltlve devlatlon; for all the other systems the deviations are negative.
Glossary experimental W n g temperature at pressure P', O C CoCTBcted boiHng temperature at normal pressure Po = 760 mmHg liquid-phase mole fraction vapor-phase mole fraction molar gas constant, 4.187 J mol-' K-I mohr volume, cm3 mol-' molar excess Glbbs energy, J mol-' NRTL model parameters, J mol-' Gothard model parameters Greek Letters third parameter in NRTL equation "I! activity coefficient in liquid phase Yl Wilson parameters, J mol-' All, XI!
Subscripts i, j components RWgkrtv NO, CH8SiHCI2, 75-54-7; (CH,)$W
75-77-4; (CH3)2SICI2,
75-78-5: CH,SiCI3, 75-79-6 SiCI,, 10026-04-7.
Literature Cited Haia, E.;Pick, J.; Vilim, 0. Vapor-LiquU EquUIbrim; Pergamon Press: Oxford, 1967. Smith, A. L. Analysis of Sllcones. Chemical Anelysls; John Wiby 6. Sons: New York. 1974; Vol. 41, Chapter 9, Yoshikawa, Y.; Tagaki. A.; Kato, M. J . Chem. Eng. Data 1980. 25, 344. ReM, R. C.; Prausnitz, J. M.; Poling, B. E. The propertkw of Oeses 6 Liquids; McGraw-Hill Book Co.: New York. 1987. Wilson, 0. M. J . Am. Chem. Soc.1964, 66. 127. Renon, H.; Prausnitz, J. M. A I C K J . 1975, 14, 135. Gothard, F. I n d . Eng. Chem. Fundem. 1985, 24, 330. Jenkins, A. C.; Chambers, G. F. I n d . Eng. Chem. 1954, 46, 2367. Mddcanov, I. K.; Korablina, T. P.; Kleinovskaya, M. A. Separadbn of Mixtures of Orgmoskon Compounds (in Russian); Khlmiya: Moscow, 1974. Received for review September 5, 1990. Revised June 17, 1991. Accepted December 3, 1991.
